高效液相色谱-质谱法测定健美类化妆品中咖啡因等33种成分

doi:10.3969/j.issn.2097-2806.2023.05.014

摘要/Abstract

摘要：

建立高效液相色谱-质谱法筛查化妆品中咖啡因等33种成分的分析方法。样品经甲醇溶解提取，高速离心后，经0.22 μm滤膜过滤，采用Atlantis^™dC18（2.1 mm×100 mm×3 μm）色谱柱分离，0.1%甲酸水溶液-乙腈为流动相进行梯度洗脱，柱温为30 ℃，流速0.3 mL/min，基质加标标准曲线测定咖啡因等33种成分。结果表明，咖啡因等33种成分在相应的质量浓度范围内线性关系良好，相关系数（r）均大于0.99；回收率为80.7%~118.2%，相对标准偏差（RSDs）均小于10%，检出限为0.003~0.015 μg/g。该方法操作简单、快速，适用于健美类化妆品中咖啡因等33种成分的检测。

关键词: 高效液相色谱-质谱法, 健美类化妆品, 非法添加

Abstract:

Bodybuilding products are also known as slimming products or anti-cellulite products, produced body shaping and bodybuilding. Through massage and hot compresses, the active substances of cosmetics are absorbed into the body, which help to decompose subcutaneous lipolysis, accelerate subcutaneous fat metabolism, and reduce edema. Due to the special way of use, large use area, and long stay time, the potential safety risks have been paid more and more attention by the consumers. There is a high risk that it may add prohibited substances. Currently, there is little literature on the determination of slimming drugs in bodybuilding products. Therefore, it is necessary to establish a method for the determination of components in these products. In this paper, an effective method of high performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS） was established for the determination of 33 kinds of components such as caffeine in bodybuilding products. The samples were extracted using methanol, and filtered through a 0.22 μm filtering membrane after centrifugation with high speed. The analysis was performed on an Atlantis^™dC18（2.1 mm×100 mm×3 μm）at 30 ℃ with 0.1% formic acid-acetonitrile as the mobile phase by gradient elution at the flow rate of 0.3 mL/min. The matrix curve was quantified by external standard method. The results show that the method has good linearity with correlation coefficients exceeding 0.99. The recoveries at different concentrations are between 80.7%-118.2%, and the relative standard deviations （RSDs） are less than 10%. The limit of detections （LODs） are 0.003-0.015 μg/g. The method proves to be simple, rapid, suitable for the determination of caffeine and others in bodybuilding products.

Key words: HPLC-MS/MS, bodybuilding products, illegally added

中图分类号:

TQ658

姜成君, 吴志珊, 殷帅, 黄海萍. 高效液相色谱-质谱法测定健美类化妆品中咖啡因等33种成分[J]. 日用化学工业（中英文）, 2023, 53(5): 588-595.

Jiang Chengjun, Wu Zhishan, Yin Shuai, Huang Haiping. Determination of 33 kinds of components such as caffeine in bodybuilding products by liquid chromatography-tandem mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2023, 53(5): 588-595.

图/表 7

表 1

33种成分的质谱信息"

编号	成分	CAS No.	分子式	离子类型	母离子（m/z）	质量数（m/z）	锥孔电压/V	碰撞能量/V
1	苯丙醇胺	37577-28-9	C₉H₁₃NO	[M+H]⁺	152.1	134.1*/117.1	50	15/23
2	去甲伪麻黄碱	37577-07-4	C₉H₁₃NO	[M+H]⁺	152.1	134*/117	50	9/21
3	麻黄碱	299-42-3	C₁₀H₁₅NO	[M+H]⁺	166.1	148*/116.9	50	15/28
4	伪麻黄碱	321-97-1	C₁₀H₁₅NO	[M+H]⁺	166.1	148*/117	50	9/21
5	甲基麻黄碱	552-79-4	C₁₁H₁₇NO	[M+H]⁺	180.1	162.1*/147	50	19/26.5
6	安非他明	300-62-9	C₉H₁₃N	[M+H]⁺	136.1	91*/119	70	23/12
7	甲基安非他明	4846-07-5	C₁₀H₁₅N	[M+H]⁺	150.1	91*/119	50	30/15
8	咖啡因	58-08-2	C₈H₁₀N₄O₂	[M+H]⁺	195.1	138*/110.1	50	26/30
9	分特拉明	122-09-8	C₁₀H₁₅N	[M+H]⁺	150.1	91*/133	50	28/13
10	氯卡色林	616202-92-7	C₁₁H₁₄ClN	[M+H]⁺	196.1	128.9*/144.1	50	43/29
11	安非他酮	34841-39-9	C₁₃H₁₈ClNO	[M+H]⁺	240.1	184*/131	50	17/37
12	芬氟拉明	458-24-2	C₁₂H₁₆F₃N	[M+H]⁺	232.1	158.9*/187	50	29/19
13	吲达帕胺	26807-65-8	C₁₆H₁₆ClN₃O₃S	[M+H]⁺	366.1	132.1*/117.1	70	24/60
14	酚酞	77-09-8	C₂₀H₁₄O₄	[M+H]⁺	319.1	225.1*/140.9	140	30/54
15	N，N-双去甲基西布曲明	84467-54-9	C₁₅H₂₂ClN	[M+H]⁺	252.2	124.9*/138.9	50	33/15
16	氟西汀	54910-89-3	C₁₇H₁₈F₃NO	[M+H]⁺	310.1	44.2*/148	50	50/12
17	N-单去甲基西布曲明	168835-59-4	C₁₆H₂₅ClN	[M+H]⁺	266.2	124.9*/138.9	50	35/19
18	比沙可啶	603-50-9	C₂₂H₁₉NO₄	[M+H]⁺	362.1	183.9*/226	50	38/25
19	西布曲明	106650-56-0	C₁₇H₂₆ClN	[M+H]⁺	280.2	124.9*/138.9	50	45/21
20	苄基西布曲明	1446140-91-5	C₂₀H₂₄ClN	[M+H]⁺	314.2	91*/124.9	50	50/27
21	豪莫西布曲明	935888-80-5	C₁₈H₂₈ClN	[M+H]⁺	294.2	124.9*/138.9	50	42/22
22	氯代西布曲明	766462-77-5	C₁₇H₂₅Cl₂N	[M+H]⁺	314.2	159*/172.8	50	40/22
23	苯扎贝特	41859-67-0	C₁₉H₂₀ClNO₄	[M+H]⁺	362.1	138.9*/316.1	50	39/20
24	布美他尼	28395-03-1	C₁₇H₂₀N₂O₅S	[M+H]⁺	365.1	240*/184.1	50	24/32
25	洛伐他汀	75330-75-5	C₂₄H₃₆O₅	[M+H]⁺	405.3	285.1*/184.1	50	17/16
26	辛伐他汀	79902-63-9	C₂₅H₃₈O₅	[M+H]⁺	419.3	285*/199.1	80	15/17
27	利莫那班	168273-06-1	C₂₂H₂₁Cl₃N₄O	[M+H]⁺	463.1	362.8*/84.1	50	42/30
28	非诺贝特	49562-28-9	C₂₀H₂₁ClO₄	[M+H]⁺	361.1	233*/138.9	50	24/40
29	奥利司他	96829-58- 2	C₂₉H₅₃NO₅	[M+H]⁺	496.4	319.2*/337.1	95	17/17
30	氯噻嗪	58-94-6	C₇H₆ClN₃O₄S₂	[M-H]^-	293.9	214*/178.7	-105	-40/-61
31	氢氯噻嗪	58-93-5	C₇H₈ClN₃O₄S₂	[M-H]^-	296	268.8*/204.9	-105	-27/-31
32	普伐他汀	81093-37-0	C₂₃H₃₆O₇	[M-H]^-	423.2	303.1*/321.2	-105	-23/-20
33	呋塞米	54-31-9	C₁₂H₁₁ClN₂O₅S	[M-H]^-	329	284.9*/205	-105	-22/-30

表 1

图 1

图 2

表 2

表 3

33种成分的保留时间、线性范围、回归方程、相关系数、检出限和定量限"

编号	成分	保留时间/min	线性范围/（μg/L）	线性方程	相关系数	检出限/（μg/g）	定量限/（μg/g）
1	苯丙醇胺	3.82	1~10	y=1.296 33×10⁵x-5 606.682 99	0.997 4	0.015	0.05
2	去甲伪麻黄碱	4.03	1~10	y=1.301 44×10⁵x+5.233 80×10⁴	0.993 5	0.011	0.04
3	麻黄碱	4.49	1~10	y=8.514 93×10⁵x+3.757 64×10⁵	0.998 7	0.004	0.01
4	伪麻黄碱	4.53	1~10	y=8.026 52×10⁵x+2.059 71×10⁵	0.999 5	0.004	0.01
5	甲基麻黄碱	4.77	1~10	y=3.674 27×10⁵x-12 204.745 36	0.999 5	0.014	0.05
6	安非他明	4.93	1~10	y=6.050 6×10⁴x+1.076 43×10⁵	0.998 5	0.005	0.02
7	甲基安非他明	5.36	1~10	y=9.106 58×10⁵x-4.431 63×10⁵	0.996 4	0.009	0.03
8	咖啡因	5.68	1~10	y=1.127 81×10⁵x+1.032 58×10⁵	0.994 7	0.004	0.01
9	分特拉明	5.62	1~10	y=1.668 13×10⁵x+1.709 63×10⁵	0.999 1	0.033	0.10
10	氯卡色林	7.28	1~10	y=1.703 01×10⁵x+1.239 12×10⁵	0.993 6	0.006	0.02
11	安非他酮	7.46	1~10	y=5.285 79×10⁴x+3.907 80×10⁴	0.995 5	0.009	0.03
12	芬氟拉明	7.86	1~10	y=9.030 86×10⁵x+4.222 32×10⁵	0.998 7	0.006	0.02
13	吲达帕胺	10.23	1~10	y=1.368 8×10⁵x-81 050	0.996 3	0.009	0.03
14	酚酞	10.34	1~10	y=2.107 87×10⁵x+1.654 12×10⁵	0.996 8	0.004	0.01
15	N，N-双去甲基西布曲明	9.33	1~10	y=2.940 38×10⁵x+1.610 53×10⁵	0.997 1	0.005	0.02
16	氟西汀	9.52	1~10	y=4.063 84×10⁵x+4.119 10×10⁵	0.997 8	0.005	0.02
17	N-单去甲基西布曲明	9.48	1~10	y=7.463 78×10⁵x+3.548 24×10⁵	0.996 8	0.006	0.02
18	比沙可啶	10.32	1~10	y=9.701 58×10⁵x+5.211 52×10⁵	0.993 9	0.004	0.01
19	西布曲明	9.66	1~10	y=7.955 45×10⁵x+2.769 37×10⁵	0.998 7	0.003	0.01
20	苄基西布曲明	9.87	1~10	y=7.163 31×10⁵x+2.959 66×10⁵	0.998 5	0.004	0.01
21	豪莫西布曲明	9.90	1~10	y=9.217 86×10⁵x+1.718 85×10⁵	0.998 2	0.004	0.01
22	氯代西布曲明	10.11	1~10	y=4.085 04×10⁵x+1.338 18×10⁵	0.998 2	0.006	0.02
23	苯扎贝特	11.35	1~10	y=1.542 06×10⁵x+8.276 36×10⁴	0.995 0	0.009	0.03
24	布美他尼	11.44	1~10	y=9.354 70×10⁴x+4.942 09×10⁴	0.992 6	0.005	0.02
25	洛伐他汀	12.99	1~10	y=13 758.507 08x+11 439.274 85	0.997 1	0.01	0.03
26	辛伐他汀	13.31	1~10	y=9 985.675 77x+3 623.576 64	0.991 6	0.014	0.05
27	利莫那班	13.41	1~10	y=6.371 39×10⁵x+9.509 67×10⁴	0.997 4	0.005	0.02
28	非诺贝特	13.62	1~10	y=2.880 53×10⁵x+1.607 13×10⁵	0.997 9	0.005	0.02
29	奥利司他	15.58	1~10	y=1.185 01×10⁵x+7.922 23×10⁴	0.995 3	0.006	0.02
30	氯噻嗪	2.75	5~50	y=15 806.631 83x+20 430.762 11	0.998 8	0.003	0.01
31	氢氯噻嗪	2.89	5~50	y=6.050 67×10⁴x+1.076 43×10⁵	0.999 1	0.006	0.02
32	普伐他汀	4.95	5~50	y=13 401.885 62x+26 047.007 41	0.998 5	0.006	0.02
33	呋塞米	5.23	5~50	y=3.007 55×10⁴x+8.954 48×10⁴	0.997 6	0.005	0.02

表 3

表 4

表 5

参考文献 8

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编号	成分	乳剂	霜剂	凝胶剂	油剂	编号	成分	乳剂	霜剂	凝胶剂	油剂
1	苯丙醇胺	90.2	79.5	83.8	102.9	18	比沙可啶	95.3	31.5	98.5	126.8
2	去甲伪麻黄碱	86.5	82.1	78.1	111.9	19	西布曲明	41.7	101.6	92.1	104
3	麻黄碱	57.4	59.7	58.9	89.3	20	苄基西布曲明	55.9	94.1	88.3	95.9
4	伪麻黄碱	60.2	63.3	62.9	93.4	21	豪莫西布曲明	61.9	94.9	91.7	101.2
5	甲基麻黄碱	75.3	97.2	84	99.7	22	氯代西布曲明	78.5	94.4	86.4	95.8
6	安非他明	63.2	62.5	63.9	79.2	23	苯扎贝特	104.6	111.7	99.6	120.1
7	甲基安非他明	50.2	47.8	55.5	79.9	24	布美他尼	117.4	117.5	107.4	108.5
8	咖啡因	80.2	84.4	98.5	94.9	25	洛伐他汀	95.8	78.9	146.5	212
9	分特拉明	77.4	84.9	85.5	114.6	26	辛伐他汀	101.8	81.5	174.6	184.4
10	氯卡色林	8.6	8.6	27.4	86.5	27	利莫那班	86.3	147.3	171	125.5
11	安非他酮	43.9	91.1	83.7	104.8	28	非诺贝特	73	151	149.2	103.2
12	芬氟拉明	52.9	88.9	80.3	102.1	29	奥利司他	51.5	59.1	135.9	91.7
13	吲达帕胺	121.8	138.5	126.5	144.5	30	氯噻嗪	81.2	104.1	91.7	85.9
14	酚酞	113.7	119.5	113.5	130.9	31	氢氯噻嗪	83.5	89.9	85.6	86.1
15	N，N-双去甲基西布曲明	80.2	97.7	96.3	122.7	32 33	普伐他汀呋塞米	90.2 99.1	94.9 109.5	89.9 100.8	89.7 93.5
16	氟西汀	20.1	23.4	65.2	111.9	32 33	普伐他汀呋塞米	90.2 99.1	94.9 109.5	89.9 100.8	89.7 93.5
17	N-单去甲基西布曲明	45.7	91.5	89.3	112.7